The present invention relates to monohydroxyl polyfluorooxetane oligomers and polymers. The present invention further relates to radiation curable coatings made from functionalized polyfluorooxetane oligomers or polymers.
Traditionally radiation curable coatings utilized combinations of silicone oils, wetting agents and polyethylene waxes to provide smoothness, abrasion resistance, low friction and scratch resistance. However these materials can be largely fugitive in nature and thus migratory leading to handling problems, lowering durability, and possibly working at cross-purposes leading to decreases in other coating properties such as gloss.
U.S. Pat. No. 5,411,996 disclosed the use of fluoroalcohol in U. V. epoxy-silicone coating formulations. The fluorinated alcohols were used to solubilize the U. V. initiator (sulfonium salt) to allow the polymerization reaction to occur.
U.S. Pat. No. 5,081,165 related to an anti-fouling coating composition comprising a photopolymerization initiator or thermal polymerization initiator and fluorine containing (meth)acrylate.
U.S. Pat. No. 4,833,207 relates to a curable composition for forming a cladding for an optical fiber having a refractive index of about 1.43 to 1.60.
U.S. Pat. No. 5,674,951 discloses isocyanate functionalized polyoxetane polymers with pendant fluorinated side chains that can optionally be chain extended with polyoxetanes or other polyethers, have the isocyanate group blocked, and be crosslinked into a network. These coatings were effective for glass run channels.
Monoalcohols are reacted with fluorooxetane monomers to produce monohydroxyl polyfluorooxetane oligomers and polymers utilizing cationic catalysts. The polyfluorooxetane oligomers and polymers can be reacted with cyclic ethers, or they can be functionalized with various end groups and thereafter used in a radiation curable coating composition. Generally, the oligomer or polymer can contain various functional groups such as acrylate, methacrylate, or a less reactive allylic, or other functional groups such as melamine, amine, epoxide, silyl, isocyanate, aceteyl acetate, and the like. These polyfluorooxetanes can be called fluorinated polyoxetanes or polyoxetanes with partially fluorinated pendant side groups (chains). These fluorinated oxetane repeating units have a single pendant fluorinated side group per repeating unit or they can have two pendant fluorinated side groups per repeating unit. The coating composition comprises the functionalized oligomer or polymer, a comonomer, optional UV initiator, crosslinking agents, and optionally other additives like pigments, plasticizers, rheology modifiers etc.
The functionalized polyfluorooxetane can be produced by several methods, but due to the reactivity of the hydroxyl groups of the polyfluorooxetane it is desirable to sequentially add the reactants so nearly complete functionalization of the polyfluorooxetane can be achieved. Typically, an isocyanate or epoxy functionalize polyfluorooxetane is first formed and that is reacted with a compound which will yield a functionalized polyfluorooxetane with intervening urethane linkages or linkages derived from the epoxy compound. Alternatively the functionalizing compound can be reacted with epoxy or isocyanate and the resulting compound then reacted with the polyfluorooxetane. Alternatively the fluorinated polyol may be made through tranesterification or an unsaturated alcohol may be used in the initiation step for the formation of the mono-functional fluorinated material.
Generally, any type of monoalcohol can be utilized to produce the monohydroxyl polyfluorooxetane (MOX) oligomers or polymers of the present invention. The monoalcohol generally has from 1 to about 40 and preferably from about 1 to about 18 carbon atoms. Examples of specific types of monohydric alcohols include the various aliphatic alcohols such as the paraffinic alcohols, for example methyl alcohol, ethyl alcohol, propyl alcohol, etc., or the olefinic alcohols, for example vinyl alcohol, allyl alcohol, and the like. Various alicyclic alcohols such as cyclohexanol and the like can be utilized, as well as various aromatic alcohols such as benzyl alcohol, phenol, and the like. Various heterocyclic alcohols can also be utilized such as furfuryl alcohol, and the like. Moreover, halogenated alcohols and especially fluoroalcohols are desired such as trifluoroethanol, heptafluorobutanol, and the like. Especially preferred monohydric alcohols include benzyl alcohol, trifluoroethanol, heptafluorobutanol, and allyl alcohol.
The oxetane monomer used to form the polyfluorooxetane has the structure 
and the repeating unit derived from the oxetane monomer has the formula: 
where each n is the same or different and independently, is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and individually is an oxaperfluorinated polyether having from 4 to 60 carbon atoms. The amount of the fluorooxetane monomers utilized is sufficient to yield a degree of polymerization (DP) of from about 2 to about 150, desirably from about 3 to about 50, and preferably from about 12 to about 25.
Generally any suitable cationic catalyst can be utilized to polymerize the fluorooxetane monomers such as various Lewis acids and complexes thereof. Examples of such cationic catalysts include Sn(IV)Cl4, antimony pentafluoride, phosphorous pentafluoride, and the like, with a complex of borontrifluoride and tetrahydrofuran being preferred. Optionally, various co-catalysts can be utilized such as water, butanediol, cyclohexanedimethanol, and the like.
The homopolymerization is generally carried out in the presence of a catalyst as well as in a solvent for the monoalcohol and the fluorooxetane monomer. Examples of suitable solvents include trifluorotoluene, dichloroethane, dimethylformamide, as well as dichloromethane. The amount of the alcohol and catalyst will generally vary inversely with the desired molecular weight of the polymer. That is, the polymerization is initiated by each alcohol and catalyst molecule generally on a quantitative basis for a given amount of fluorooxetane monomer, hence, the molecular weight of the polyfluorooxetane oligomer or polymer will be determined by the amount of alcohol utilized.
The reaction rate will vary with temperature. Accordingly, the react on time is generally from 2 hours to 40 hours, and desirably is from about 4 to about 24 hours. The polymerization temperatures are generally from about 0xc2x0 C. up to about 100xc2x0 C., and desirably from about 18xc2x0 C. to about 50xc2x0 C. Lower reaction temperatures result in very slow reaction rates, whereas higher reaction temperatures can enhance the formation of cyclic structures containing from 3 to 4 oxetane units. As noted, monomer conversion to polymer is essentially quantitative. The monohydroxyl polyfluorooxetane oligomers or polymers produced are washed with water to obtain a neutral pH and the water removed as by decanting. Subsequently, any suitable desiccant can be utilized such as calcium chloride, phosphorous pentoxide, calcium carbonate, magnesium sulfate, molecular sieves, to dry the oligomers or polymers.
The monofunctional polyfluorooxetane oligomers or polymers generally have the formula: 
where xe2x80x9cnxe2x80x9dR, Rf and DP are as described hereinabove and R1 is the organic group of the reactive monoalcohol. That is, R1 can be an aliphatic group such as a paraffinic group or an olefinic group, or an alicyclic group, or an aromatic group, or a heterocyclic group, or a halogenated organic group, and the like, having from 1 to about 40 and preferably from 1 to about 18 carbon atoms. If more than one type of monoalcohol is utilized to prepare the polyfluorooxetane oligomers or polymers, naturally the R1 of one or more different polymers or oligomers will be different.
The monofunctional polyoxetane oligomers or polymers can be used in a variety of ways such as surface modifiers, in coatings, in polymer blends and alloys, within interpenetrating polymer networks, as well as in block and graft copolymers.
The fluorooxetane monomers can also be copolymerized with a variety of monomers having epoxy (oxirane) functionality such as epichlorohydrin, propylene oxide, ethylene oxide, butyl glycidylether, and perfluorooctyl propylene oxide; monomers having a 4-membered cyclic ether group such as trimethylene oxide, 3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, and, 3,3-bromomethyl(methyl)oxetane; monomers having a 5 membered cyclic ether group such as tetrahydrofuran, tetrahydropyran, and 2-methyltetrahydrofuran; and the like. Still other suitable monomers include 1,4-dioxane, 1,3-dioxane and 1,3-dioxalane as well as trioxane and caprolactone. The copolymerization reaction is carried out generally under the same conditions as is the polymerization of the fluorooxetane monomers set forth hereinabove. The amount of the comonomer is from about 0.1% to about 99% by weight, desirably from about 1.5% to about 50% by weight, and preferably from about 2% to about 10% by weight based upon the total weight of the one or more comonomers and the fluorooxetane monomers.
A primary use of the monohydric polyfluorooxetane oligomers and polymers (alcohols) is to functionalize the same with various functional end groups for subsequent use. Such functional end groups include acrylate, methacrylate, allylic, melamine, amine, aceteyl acetate, epoxide, silyl, isocyanate, and the like. Such end groups can be derived from a variety of compounds known to the art and to the literature. For example, acrylate end groups can be derived from hydroxyethyl acrylate, methacrylate end groups can be derived from hydroxymethyl methacrylate, allylic end groups can be derived from allylchloride, melamine end groups can be derived from Cymel 303, amine end groups can be derived from hexamethylene diamine, epoxide end groups can be derived from glycidal methacrylate, silyl end groups can be derived from chlorotrimethylsilane, and isocyanate end groups can be derived from isophorone diisocyanate. Hereinafter, the term xe2x80x9cfunctionalizedxe2x80x9d polyfluorooxetane oligomers and polymers are meant to include such end groups. The polyfluorooxetanes of the present invention can also be called fluorinated polyoxetanes or polyoxetanes with partially fluorinated pendant side groups (chains). These pendant side groups include the Rf groups defined later. The amount of the functionalizing compounds is from about 1.0 to about 1.2, and preferably from about 1.0 to about 1.05 weight equivalents. The reaction temperature will vary from about 10xc2x0 C. to about 120xc2x0 C. and preferably from about 65xc2x0 C. to about 90xc2x0 C. Reaction time will generally vary with the temperature and with the reactivity of the components.
The coating composition of the present invention comprises a functionalized polyfluorooxetane oligomer or polymer, a comonomer, optionally a UV initiator, crosslinking agents, and optionally other additives such as pigments, plasticizers, rheology modifiers etc. While the functionalized polyfluorooxetane can be used in about any concentration in the radiation curable coating it is generally effective in an amount of repeating units of the illustrated formula from about 0.05, or from about 0.1, or from about 1 to about 10 or 20 weight percent based on the weight of the coating composition.
The various functionalized polyfluorooxetanes can be produced by several methods, but due to the lower reactivity of the hydroxyl groups of the polyfluorooxetane with isocyanate and epoxy groups, it is desirable to sequentially add the reactants so nearly complete functionalization of the polyfluorooxetane can be achieved. Typically an isocyanate or epoxy functionalize polyfluorooxetane is first formed and then reacted with a compound forming a functionalized end group such as a hydroxy alkyl acrylate, (e.g. hydroxyethyl acrylate) to form a functionalized polyfluorooxetane. In a similar manner, other compounds can be utilized to form the above noted functional end group such as methacrylate, allylic, melamine, amine, and the like. Alternatively, the compound forming the functional end group can be reacted with the epoxy or isocyanate to functionalize the same and that compound reacted with the polyfluorooxetane.
The polyfluorooxetane when incorporated into a coating via the functionalized group, e.g. acrylate, amine, etc., provides improved wear resistance, mar resistance, stain resistance, leveling, improved slip and lower coefficient of friction. There are generally enhanced surface properties relative to a coating without the additive. While not being bound by any explanation, it is anticipated that the polyfluorooxetane, to the extent possible while blended with the other components and after curing, migrates to the interfaces between the coating and the substrate and the interface between the coating and the atmosphere providing increased wetting at the solid interface improving adhesion, and lowering the surface tension at the atmosphere interface improving leveling, providing improved surfaces (gloss/appearance) at the atmosphere interface, and improved wear and stain resistance at the atmosphere interface The application is focused on coatings because molded articles and thicker compositions are more difficult to cure with radiation cures, but this does not preclude their use in thick articles.
Another focus of this application is adding the properties of the partially or fully fluorinated pendant groups without detracting from the inherent physical bulk properties typically found in vinyl ester resin acrylic, urethane acrylic and epoxy acrylic compositions. The polyoxetane in being available as a polyol can be conveniently reacted in the network via epoxy or isocyanate reactive groups which are common connecting groups in acrylic, methacrylic, vinyl ester resin and acrylic compositions.
The substrates for the radiation curable coating include thermoplastic or thermoset plastics, paper, metals, wovens and nonwovens, cellulosics other than paper, etc. Preferred plastics include polyvinyl chloride, polyolefin (surface treated and untreated), polyesters, and polycarbonates. The plastics may be formed into furniture, cabinets, flooring overlay, building products, etc. Preferred cellulosics include wood products such as furniture, cabinets, wood flooring, paper, and the like. The coating is useful as a protective coating for any of the above substrates.
The coating can be modified to be flexible or rigid depending on the flexibility of the substrate. The polarity of the coating can be adjusted by changing the polarity of the acrylate, or methacrylate, or allylic, terminated components or the monomer to make it compatible with the substrate. The coating can be made more flexible by using less crosslinking agents or choosing a comonomer that forms a lower glass transition temperature polymer. The backbone of a polyfunctional crosslinking agent polymer can also be chosen to result in a softer lower flexural modulus coating.
Various curing options are available for the coating composition. As shown in the examples some of the components cure upon standing if polymerization inhibitors are not present. Electron beam irradiation can be used to cure the coatings. If ultraviolet (UV) activated free radical photoinitiators are present, ultraviolet light can activate curing. When UV cure is utilized, the functionalized end groups can be acrylate, methacrylate, allylic, or epoxide. Thermal cure can also be utilized and in this situation the functionalized groups include melamine, amine, acetylacetate, silyl, isocyanate, and epoxide. Combinations of two curatives of a single type can be used. The amount and types of curatives are well known to the art of radiation and UV curatives. The amount of curatives is that which converts at least 50, 75 or 90 or even 100 weight percent of the polymerizable components of the coating into nonextractable gel. The polymerization conditions for the coating composition are generally the same as set forth above with regard to copolymerizing polyfluorooxetane monomers with cyclic ethers. That is, any suitable cationic catalyst can be utilized such as a complex of borontrifluoride and tetrahydrofurane, the polymerization being carried out in the presence of a polar solvent such as dichloromethane, reaction rate varying with temperature, and the like, all of which is set forth hereinabove and incorporated by reference.
The comonomers that can be used in the coating are generally any unsaturated monomers copolymerizable through said functionalized polyfluorooxetane. Comonomers can be distinguished from the later described crosslinking agents such as polyfunctional acrylate oligomers by the fact that comonomers are generally monofunctional and form a linear polymer while polyfunctional reactants form crosslinked polymers. Comonomers include unsaturated monomers such as vinyl aromatic monomers of 8 to 12 carbon atoms such as styrene, alphamethylstyrene, vinyltoluene, and the like; ethylenically unsaturated monomers generally free of acid groups having from 4 to 30 carbon atoms including acrylates such as methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate; acrylic acid, etc.; (cyclo)alkyl esters of maleic acid, fumaric acid and itaconic acid, for example dimethyl maleate, diethyl maleate, diethyl fumarate, dipropyl maleate, dibutyl maleate and dibutyl fumarate; (meth)acrylates containing ether groups, for example 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate and 3-methoxypropyl (meth)acrylate; hydroxyalkyl (meth)acrylates, for example 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; hydroxypolypropylene glycol (meth)acrylates, and the like; and N-vinyl pyrrolidone; various conjugated dienes having from 4 to 10 carbon atoms such as butadiene, isoprene, and the like. In the above list, whenever (meth) is utilized, it means that the existence of a methyl group within the compound is optional. The monomer(s) are generally utilized in any desired amount and selected based upon a variety of considerations including volatility, relative health hazards from exposure, their reactivity ratios in copolymerization with the acrylate terminated polymers and oligomers, etc.
One type of crosslinking agents are the various polyfunctional oligomers and polymers (other than the monofunctionalized polyfluorooxetane) utilized in radiation curable coatings. They are characterized by the presence of two or more unsaturated carbon to carbon double bonds that can copolymerize with the comonomer(s). These components are added in effective amounts to change the physical properties of the coatings such as crosslink density, which has an effect on modulus and strength. These reactants contribute significantly to the solvent resistance of the cured coatings as the crosslinks they provide inhibit swelling in common solvents. Examples of such crosslinking agents include Ebecryl 810, TRPGDA, tripropylene glycol diacrylate; and TMPTA, trimethylolpropane triacrylate. Crosslinking agents also include oligomeric polyunsaturated compounds which act not only as crosslinking agents, but also contribute to the overall performance of the UV curable coating. Such compounds include acrylated or methacrylated, or allylic functionalized polyesters such as Ebecryl 81, an acrylated polyester; acrylated, or methacrylated, or allylic functionalized urethane acrylics such as Ebecryl 4883, an acrylated aliphatic urethane; acrylated or methacrylated, or allylic functionalized urethane polyesters; acrylated, or methacrylated, or allylic functionalized epoxy; or acrylated or methacrylated, or allylic functionalized epoxy polyesters.
Ultraviolet light (UV) activated curative(s) may be used in the coating in an effective amount to cause polymerization of the comonomer(s) and crosslinking by the polyfunctional oligomer and polymeric crosslinking agents. These curatives may be any chemical compound that can generate free radicals on exposure to ultraviolet radiation. UV activated curatives are set forth in U.S. Pat. Nos. 5,411,996; 4,882,201 and 4,279,717 herein incorporated by reference. Other UV activated curatives such as Cyracure UVR-6110 and Cyracure UVI-6974 used in the examples are commercially available and known to the art.
Other components of the coating include fillers such as TiO2, and zinc oxide, as well as other pigments and colorants; metallic pigments such as aluminum flakes; antigloss agents such as precipitated and organic silicas; dyes; plasticizers such as ester oils, triglycerides, hydrocarbon oils; calcium carbonate; clay; talc; waxes; flow modifiers such as rheology modifiers, shear thinning agents; accelerators or coinitiators such as amines, and wetting agents and surface modifiers for fillers.
The oxetane polymer (including copolymers, terpolymers, etc.) generally have one hydroxyl group although two or more terminal hydroxyl groups are possible for these polymers. Molecules with two or more hydroxyl groups are generally referred to as polyols. Monohydric alcohols refers to alcohols with only one hydroxyl group. These alcohols desirably have degrees of polymerization from about 2, 3, or 4 to about 150, more desirably from about 3 to about 100 and preferably from about 3 to about 30 or 50. Desirably they have from about 1 hydroxyl group per molecule although a trace of polyols can be accepted as they do not interfere with the properties as shown in the examples.
The reactivity of the polyfluorooxetane with isocyanate groups and with epoxy groups is generally not as good as the reactivity of conventional polyethers such as poly(ethylene oxide) with isocyanates and epoxies. Therefore it is desirable to control the reaction sequence and reaction ratios to maximize the functionalization of the polyfluorooxetane with the isocyanate or epoxy groups and then with the acrylate, methacrylate, or amine, etc., functionality.
One procedure is to first react the polyfluorooxetane with the di or polyisocyanate or di or poly epoxy compound to generate (form) isocyanate or epoxy groups on the end (terminusi) of the polyfluorooxetane (isocyanate or epoxy terminated polyfluorooxetane). Catalysts and or other favorable reaction conditions (heating) may be employed to force this reaction towards completion.
The reaction between the hydroxy group and the isocyanate or epoxy group can be monitored by various chemical analysis methods to optimize reaction conditions. Desirably at least 2 moles of isocyanate groups or epoxy groups are present for every mole of hydroxyl group. This promotes end capping of the monohydric polyfluorooxetane rather than chain extension, which is the predominant reaction when the ratio of isocyanate or epoxy groups to hydroxyl groups is 1:1. In most embodiments chain extension is not desirable as the resulting higher molecular weight polymers increase the coating viscosity and may decrease the number of load bearing chains, which can decrease physical properties. Desirably the moles of isocyanate groups or epoxy groups is between 2 and 3 per mole of hydroxyl groups and more desirably between 2.0 and 2.5. Other reaction conditions can be optimized to further limit chain extension.
After an isocyanate or epoxy terminated polyfluorooxetane is formed it can be reacted with a functionalizing compound yielding the above noted functional group such as an acrylate, or methacrylate, or allylic, etc. As noted above, hydroxyalkyl acrylates, such as hydroxyethyl acrylate or hydroxyethyl (alk)acrylate are preferred as the hydroxyl groups forms a very chemically stable urethane linkage. The use of xe2x80x9c(alk) before acrylate is used to indicate the optional inclusion of alkyl substituents of 1 to 6 carbon atoms. Other acrylate, etc., functional monomer(s) that can be attached to the isocyanate or epoxy functionalized polyfluorooxetane as noted above include amine functional acrylates, acrylamides, or acrylic acids, and the like.
Another way to achieve the same result is to react the di or polyfunctional isocyanate or epoxy compound with the compound yielding the acrylate, methacrylate, allylic, etc. functional group in a mole ratio of isocyanate or epoxy groups to the functional forming compound (e.g. hydroxyl) of above 2, more desirably from about 2 to 3 and preferably about 2 to about 2.5. This will form an isocyanate or epoxy functionalized acrylate, or methacrylate, or allylic, etc. One such reaction product, glycidyl methacrylate, is commercially available. These isocyanate or epoxy functional acrylates, or methacrylates, or allylics, etc., can be reacted with the polyfluorooxetane to produce a monofunctionalized (acrylate, etc.) polyfluorooxetane.
The di- or polyisocyanate compound can generally be any compound of the formula X-(NCO)y where y is an integer above 2 and X is an aliphatic group of 4 to 100 carbon atoms, an aromatic group of 6 to 20 carbon atoms, or a combination of alkyl and aromatic groups or alkyl substituted aromatic or aromatic substituted alkyl of 7 to 30 carbon atoms or oligomers thereof. These isocyanate compounds are well known to the art. Preferred ones are 4xe2x80x2,4-methylene diphenyl isocyanate (MDI) as well as polymeric MDI, which is a liquid rather than a crystalline solid, toluene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate (preferred), trimethylhexane diisocyanate, etc.
Similarly the epoxy compounds can generally have the formula: 
where y is as previously defined and Z is a di or polyvalent group having from 2 to 100 carbon atoms, often 1 or more oxygen atoms, and sometimes other heteroatoms besides oxygen and hydrogen. It is desirable to keep the molecular weight of the epoxy compound as low as higher molecular weights will increase the viscosity